Silver halide developers for the production of azine dyestuff images



Patented Oct. 24, 1950 SILVER HALIDE DEVELOPERS FOR THE PRODUCTION OF AZINE DYESTUFF IMAGES Willy A. Schmidt and Robert C. Gunther, Easton,

- Pa., assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware N Drawing.

Application July 15, 1948,

Serial No. 38,948

5 Claims.

The present invention relates to the production of azine dye images and more particularly to color developers designed to yield such images of good gradation and dye density and free from color fog.

In the conventional mechanism of color forming development, an aromatic primary amine is employed to reduce an exposed silver halide image to metallic silver,"the amine being thereb oxidized to a component which couples with a color former to produce a dyestuff image in situ with the metallic silver image. To date all color forming development processes which have been commercialli exploited have as the developer an NN-dialkylated-pphenylene diamine. Such developers have been used for development of a latent image as well as for the development of a residual silver halide image in the reversal process.

Schmidt and Tulagin, in'their application Se-, rial No. 640,382, filed January 10, 1946, now Patent No. 2,486,440, disclosed that azine dye images can be obtained by developing an exposed silver halide emulsion with developers of the 2.4-diamino aniline type, and particularly those of the class of the N-substituted 4.6-diamino metanilic acids. The azine dye images which result from this method are much more stable to acids, alkalies and alkaline oxidation than are the azo halide which does not azine dye forming color developers. getic latent image developers contemplated herein are those generally referred to in color photography as silver developers or black and white{ developers.

The partial development effected by the energetic latent image developer may be realizedby bathing the exposed silver halide in such a developer for a short period of time and then de-} between the energetic latent image developer andthe color developer has not been ascertained. It was our original theor that the energetic. latent image developer operated as a catalyst on accelerator for the color developer in the devel opment of a latent image. This theory, however, would not explain the fact that the film can be washed for hour or longer after an extremely shorttreatment with the energetic developer and the latent image still be capable of being com: pletely developed by the color developer. It is our opinion, therefore, that the energetic or black and white developer leads to an intensimethine and quinonimine dyes produced with the fication of the latent image or produces silver generally employed p-phenylene diamine type nuclei or development centers which aid or facildevelopers. t I v itate the reduction of additional exposed silver One of the difiiculties which has been. enhalide by the azine dye forming color developer. countered in the production of azine dye images it is accordingly an object of the present inby color-development resides in the fact that vention to produce uniformly and energetically while some 2.4-diamino anilines are capable of azine dyestuff images with. an azine dye formdeveloping a latent image, a large number of ing color developer by carrying out a portion of them are unsatisfactory; yielding either, no im the development with an energetic latent image ages at all or only very weak images. It has developer. Y '7 1 r been proposed to energize such development, 40 It is a further object of the present invention particularly when-developing a residual silver halide in the reversal process by use with the 2.4-

diamino aniline developers of nitrogenous bases, such as ethylenediamine, benzylamine, quinoline, and the like.

We have now ascertained that the formation of azine dye images can be uniforml and energetically effected while obtaining improved color rendition'and substantiallyno color fog bycarry ing out the development in part with an energetic to improve the azine dye images obtained by c01 or development with an azine dye-forming color developer by adding to the developer an energetic latent image developer;

A further object of the present invention is to produce azine dye images which have improved latent image developer ior the exposed silver color rendition and freedom from color fog by developing an exposed silver halide emulsion in the presence of a color formerwith a 4.6-diamino metanilic acid developer containing an en ergetic latent image developer.

necessarily take part in the color forming reactions, the complete devel-; opment being effected with one of the aforesaid The ener-w Other and further important objects will be come apparent as the description proceeds.

Compounds which may be used as the color developer in producing the azine dye images are of the 2.4-diaminoaniline type and are more particularly those having the formula:

NRRi

Y NH R2 wherein R is hydrogen or alkyl, i. e., methyl, ethyl, propyl, butyl, amyl or the like, and R1' is an aliphatic radical such as alkyl .as-above, carboxy alkyl such as carboxy methyl, carboxy ethyl and the like, hydroxy alkyl such as hydroxyethyl, hydroxy propyl and the like, sulfo alkyl such as sulfomethyl, sulfopropyl, sulfobutyl and the like, or an aromatic radical such as aryl, i. e.,"phenyl, naphthyl and the like, carboxy aryl, i. e., carboxyphenyl, carboxy naphthyl and the like, sulfo aryl, i. e., sulfophenyl, sulfonapththyl and the like, alkoxy aryl such as methoxy phenyl, methoxy naphthyl, ethoxy phenyl, butyroxy phenyl and the like, alkyl aryl such as toluyl, ethylphenyl, propylphenyl and the like, carboxy alkylaryl, such as carboxy methyl phenyl, carboxy ethyl phenyl and the like, carboxy alkoxy aryl, such as carboxy methoxy phenyl, carboxy ethoxy phenyl, hydroxy alkyl aryl such as hydroxy methyl phenyl, hydroxy ethyl phenyl and the like, and

hydroxy alkoxy aryl such as hydroxy methoxy phenyl, hydroxy ethoxy phenyl and the like, R2 is an aromatic or aliphatic radical as illustrated above, and X and Y are hydrogen, alkyl as above, sulfo or carboxy, or together represent the atoms necessary to complete a six-membered isocyclic ring system such as benzo and the like. Preferably thecompounds which are utilized are the N- substituted 4.6-diamino metanilic acids, in which case Y is hydrogen, and X is sulfo.

' Examples of compounds contemplated by the above formula and found to be satisfactory for the production of the azine dye images are:

1. 5-amino-6.8-bis- (phenylamino) -1-naphthalene sulfonic acid of the formula:

NH soln 2. 2.4-bis-(phenylamino)-aniline of the formula:

4 3. 4 (phenylamino) 6 (N-sulfo methyl-N- phenylamino) -metanilic acid.

4. 2.4-bis- (2-carboxyphenylamino) -aniline. 5. 2.4-bis-(3'-carboxyphenylamino) -ani1ine of the formula:

OOH

.COOH

6. 2.4- bis (3- carboxy- 4' methoxyphenylamino) aniline.

'7. 4.6-bis- (phenylamino) -metanilic acid. 8. -4.6-bis- (4'-methoxy phenylamino) -metanili0 acid.

13. 4-(3'-carboxy-4'-methoxy phenylamino)- 6- (4'-methoxyphenylamino) -metanilic acid.

14. 4 (4' sulfophenylamino) 6 (4' methoxyphenylamino) -metanilic acid.

15. 2.4 bis (phenylamino) 5 amino benzoic acid of the formula:

CQOH

16. 4 (4' methoxyphenylamino) 6 (3' carboxymethylphenylamino) -metanilic acid.

17. 4 (4' sulfophenylamino) 6 (3' carboxymethyl 4' methoxyphenylamino) metanilic acid of the formula:

HOaS- 01120 O OH 18. 4 (4' -methoxyphenylamino) 6 dimethylamino-metanilic acid.

19. 4 (4 sulfophenylamino) 6 dimethylamino-metanilic acid.

20. 4 (4' methoxyphenylamino) 6 (4' methylphenylamino) -metanilic acid.

5. 21. 2-sulfo ethylamino-4-(2-carboxy amino) -aniline of the formula:

phenyl- NEE-0211 8 03H 26. 4.6 bis (B hydroxy anilic acid. v I g V 27. 4 ethylamino 6 (p i hydroxyethylamino)metanilic acid of the formula: I

NHOH2CH2OH 28. 4 (carboxymethylamino) amino-metanilic acid.

29. 4 butylamino 6 (4' f3 hydroxyethylphenylamino)-metanilic acid.

30. 4 (4' carboxymethylphenylamino) 6 ethylamino-metanilic acid of the formulai 6 phenyl NHGomooon I 31. 4 methylamino 6 phenylaminu met anilic acid.

32. 4.6 bis (methylamino) metanilic acid. 33. 4 .phenyla'mino -"6 methylamino met anilic acid; The aforementioned compounds may be utilized per se as-the azine dye image developer or may be used in 'admixture to insure'the production of brilliant dye images as described in Gunthers copending application Serial No. 38.808, filed of even date herewith, entitled: Production of Azine Dye Images By Means of a Developer Containing Two N-substituted Diamino Metanilic Acids". Examples of such mixtures are:-.4-(;3- hydroxyethylamino) 6 phenylamino-metanilic acid with 4-methylamino-6sphenylamino-metanilic acid, 4.6-bis-(phenylamino) -metanilic acid with 4.6-bis-(methylamino) -metanil ic' acid. The developer components listed above may be prepared by the method described in the a'fore- -:i

said application Serial No. 640,382 and Gunther application Serial No. 793,532 filed December 23, 1947. V i

Examples of "theenergetic latent image .orblack and white developers which "aretadded to; the

. aforementioned color developers in order toeif e'c't' the desired"'mo're energetic development are p-amino phenol, p-(N-methylamino) -phen ol or a mixture thereofwith hydro'duinone, 2.4-diamino phenol and ca'techoL-g I I If the invention be practicedv by bathing an. exposed'silver halide emulsion in an energetic or black and white developer followed by complete development in an azine dye color forming developer, the development time with the former will depend on the characteristics of the developer chosen, but should not exceed one-half the'time' which is necessary to develop the silver image to maximum contrast. In this period, the exposed silver halide is so conditioned that it'becomes readily amenable to the production of azine dye images with the aforesaid color developers irrespective of the energy of said developers as measured by their effect on a latent silver halide image.

If the invention be carried out by adding the energetic or black and White developer to the color. developer, then the quantity of the former used will in no case exceed the quantity by weight of the active color developer ingredient and will dependfirst upon the particular energetic or black and white developer employed, and, second, upon th type of processing involved, 1. e., whether negative or positive. Generally speaking, the more vigorous the developing substance the smaller th amount required to produce the desired effect. Similarly where the processing is by the reversal method, a smaller quantity is usedthan where the processing involves negative development. In any case'good resultsare obtained when the concentration of energetic or black and white developer rangesfrom- .5 to 4 grams per liter of developer. Within the aforestated range an amount of .5 to 1.5. grams per liter of developer of the energetic or black and white developer is sufficient to produce the desired improvement in the reversal process. Where, however, it is desired to produce negative. azine dyesythe quantity of the energetic or black and white developer employed generally ranges from 2 to 4 grams per liter.' With these quantities, the development of a latent silver halide image ;in the presence ofa suitable color former to produce excellent color rendition and dye density and without color fog formation can be effected in from '10 to 15minutes. v

'The'color formers employed are those used in the production of color developed images,

i. e., those containingaromatic-primary amino, phenolic hydroxyl, or active methylene'groups.

Examples of such compounds'are:

5-sulfo-acetoacetanilide 3-stearoylamino-5 sulfo-acetoacetanilide 2-benzcarbamyl naphtho1-7 3.G-disulfo-B-benzsulfonylamino naphthol-l B-benzsizlfonyl amino naphthol-l 3-sulfo-6-aminonaphthol-1- .3-sulfo-6-phenylaminonaphthol-1 3-sulfo 6 -(4'- methoxy' 7 phenylamino) naphthol-l 8-hydroxy quinoline "3-su1f o-6-oleylamino-naphthol- 1 naphsultamacid 3-su1fo-7-phenylaminonaphthol-1 1 .8 bis- (benzsulfonyl amino) -naphthalene fi-brom o-flehydroxy quinoline 6-sulfo-8-hydroxy quinoline cinchoninoyl as.

7 2-methyl-4.4'-dihydroxy-7.8 benzoquinoline 2 methyl 4 -i(4"-N-tetradecyl sulfoacetamido aniline) -4-hydroxy-'l.8ebenzoquinoline.

The quinolines and benzoquinolines referredto hereinabove are described in copending applications Serial Nos."l93,534 and 793,533, now *UJS. PatentNo. 2,524,741, of Tulagin 'and'Schmidtand Tulagin and Coles, respectively.

The process utilizing the developer :composi-- tions contemplated herein may be effected in various ways. For instance, the color-forming component may be located in the developer. On the other hand, the color former in non-diffusing form may be located in the emulsion. 'Multilayer film, each layer containing a non-difiusing color former, may be used and the film developed to the desired subtractive azine dye images in a single color forming development step while :utilizing such developer compositions.

The developers, in addition to the components previously mentioned, also contain an alkali such as sodium carbonate, sodium'hydroxide, and the like. Preferably the developers will also contain the usual adjuncts such as an alkali metal bromide, i.-e., potassium bromide, sodiumbromide and the like, and an alkali metal sulfite such'as sodium sulfite and the like. In some cases it has also'been found that better results are obtained when there is present in the developer a coupling aid in the form of an organic base such as pyridine, quinoline, ethylenediamine and the like.

The following examples will serve to illustrate the invention'but it is to be understood that the invention is not restricted thereto.

Example I 4-methylamino -;'6 {phenylamino-metanilic acid grams 6 2.4-diamino phenol d 1 Sodium sulfite do 60 Ethylenediamine r cc 30 Water cc "1000 The film after development is bleached'with'a ferricyanide bleach and. fixed in an acid-hardening hypo solution. There is thus obtained- .a magenta azine :dye-image of good gradationin which the whites are perfectly clear.

Example II The procedure is the same as that of Example I excepting that the 2.4-diaminophenol is replaced by 1.5 grams of p-amino phenol per liter. of developer.

Example III A bi-pack having ared sensitive'silver bromide emulsion containing asthe cyan colorformer a compound of the followingconstitution:

81 in-the'zbottom layer, .and a green sensitive silver bromide emulsion containing as the magenta color former a compound of the following constitution:

. OH: OH fi l-0151131 (JO-JNH- in the top layer is exposed, the latent image developed to a negative silver image, re-exposed and the residual silver bromide in both layers developed for 15 minutes in a solution of" the following composition:

4 (/3- hydroxyethylamino) -6-phenylaminometanilic acid grams 6 p-(N-methylamino) phenol sulfate do 1 Potassium carbonate do 20 Sodium sulfite do 60 Potassium bromide do 10 Ethylenediamine do 5 Water cc 1000 The film after development is processed as in Example I. A colored positive containing magenta and cyan azine dye images showing excellent color rendition and freedom from color fog is thus obtained.

Example IV A photographic silver bromide emulsion is exposed'and the latent image developed to a negative silverimage. The residual silver halide is re-exposed and developed in a developer of the following composition:

4.6-bis- (phenylamino) -metanilic acid grams 4 A mixture of hydroquinone andp- (N-monomethylamino) -phenol sulfate (50 :50)

grams 1.5 Sodium carbonate do 60 Sodium sulfite; do 40 Potassium bromide do 2.5 Pyridine cc l2 8-hydroxy quinoline grams 3 Water cc 1000 The film after development is bleached;in a ferricyanide bleachandfixed in an acid-hardening hypo-solution. A positivemagenta azine dye image showing excellent color rendition and no color fog is thus obtained.

. Example V The -bi-pack referred to in Example .111 is exposed and developed for 15 minutes in a solution of the followingcomposition:

4- ('B-hydroxy ethylamino) -6-phenylaminometanilic' acid "grams 6 4-methyla'mino '6 phenylamino-metanilic acid grams 3 p-(N-methylamino) phenol sulfate do 3 'Trisodium phosphate do 40 Sodium sulfite d0 '40 Potassium Lbromide do 12.5 Hydroxylamine hydrochloride do 1 Water cc 1000 I The film= after development is fixed in an acid- ;hardening. hyposolution, ibleached in a ferricyanide bleach and again fixed. A negativecontaining brilliant magenta and cyan azine dye images is thus obtained, the whites being exceedingly clear.

Example VI A photographic silver halide emulsion layer containing an azine color former in non-diffusing form as given in Example III is exposed. It is given a short development (30 to 90 seconds) in a conventional metol-hydroquinone developer. Thereafter it is thoroughly washed for 15 minutes and the development is continued in an azine color forming developer of the following composition:

4-(13-hydroxy ethylamino) -6-phenylamino metanilic acid grams 6 4-methylamino 6 phenylamind-metanilic acid grams 3 Trisodium phosphate do 40 Sodium sulfite do 40 Potassium bromide g do 12.5 Hydroxylamine hydrochloride do 1 Water cc 1000 After development, the film is washed for 10 minutes, fixed, and the silver removed in the conventional manner. There results a negative dye image of good gradation and free from color fog.

We claim:

1. The process of producing within a light sensitive photographic silver halide emulsion layer azine dye images of good color gradation and essentially free from color fog, which comprises developing the exposed silver halide in an energetic non-staining silver image developer for not more than half the time necessary to develop the silver image to maximum contrast and completing the development in the presence of a color former with a color forming developer comprising a compound selected from the class consisting of those of the following formulae:

NRR1 NRR1 and | N112 NH:

in which R is selected from the class consisting of hydrogen and alkyl, R1 is selected from the class consisting of aliphatic and aromatic radicals, R2 is selected from the class consisting of aromatic radicals, a ring carbon atom of which is directly linked to the nitrogen atom, and aliphatic radicals a carbon atom of which is directly linked to the nitrogen atom, said carbon atom being substituted by at least two hydrogen atoms, X and Y are selected from the 10 class consisting of hydrogen, alkyl, sulfo and carboxy, and Q represents the atoms necessary to complete a six-membered isocyclic ring system.

2. The process as defined in claim 1 wherein the energetic silver image developer is added to the color forming developer solution in an amount not exceeding the quantity by weight of the color forming developer substance.

3. The process as defined in claim 1 wherein the energetic silver image developer is added to the color forming developer and in an amount ranging from .5 to 4 grams per liter of the developing solution.

4. A photographic developer for the production of azine dye images having high color rendition and free from color fog comprising an aqueous alkaline solution of a non-staining silver image developer and as the color forming developer a compound selected from the class consisting of those of the following formulae:

NRR; IIIRRi and in which R is selected from the class consisting of hydrogen and alkyl, R1 is selected from the class consisting of hydrogen, aliphatic and aromatic radicals, R2 is selected from the class consisting of aromatic radicals, a ring carbon atom of which is directly linked to the nitrogen atom, and aliphatic radicals a carbon atom of which is directly linked to the nitrogen atom, said carbon atom being substituted by at least two hydrogen atoms, X and Y are selected from the class consisting of hydrogen, sulfo and carboxy, and Q represents the atoms necessary to complete a six-membered isocyclic ring system.

5. The composition as defined in claim 4 wherein the energetic silver image developer is present in an amount of from .5 to 4 grams per liter of solution.

WILLY A. SCHMIDT. ROBERT C. GUNTHER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,954,335 Seymour Apr. 10, 1934 2,301,387 Evans et a1 Nov. 10, 1942 2,414,491 Tulagin Jan. 21, 1947 2,417,514 Neumann Mar. 18, 1947 2,449,919 Weissberger Sept. 21, 1948 

1. THE PROCESS OF PRODUCING WITHIN A LIGHT SENSITIVE PHOTOGRAPHIC SILVER HALIDE EMULSION LAYER AZINE DYE IMAGES OF GOOD COLOR GRADATION AND ESSENTIALLY FREE FROM COLOR FOG, WHICH COMPRISES DEVELOPING THE EXPOSED SILVER HALIDE IN AN ENERGETIC NON-STAINING SILVER IMAGE DEVELOPER FOR NOT MORE THAN HALF THE TIME NECESSARY TO DEVELOP THE SILVER IMAGE TO MAXIMUM CONTRAST AND COMPLETING THE DEVELOPMENT IN THE PRESENCE OF A COLOR FORMER WITH A COLOR FORMING DEVELOPER COMPRISING A COMPOUND SELECTED FROM THE CLASS CONSISTING OF THOSE OF THE FOLLOWING FORMULAE: 